Reaction product of oleic acid, sebacic acid, and triethylene tetramine



United States Patent Ofiice 3050528 Patented Aug. 21, 1062 3 050 5 g catalytic pro-oxidant metals by the addition of a chelating and inactivatin agent. These metals, which are in- ES E Q Q %%R E E troduced as impurities in the acid and amine reactants,

l catalyze degradation of the reaction product with a re- Elizabeth C. D arbon B t d P 'l' Brookline, Miss g gi a gg, f g g ff 5 tilting increase in viscosity and darkening of the product.

Cambridge Mass. 3 cmpamfion of Connecticut Even small leaks in the packing surrounding the agitator No Drawing. Filed Dec. 23, 1960,Ser.N0.78,878 shaft through which atmospheric Oxygen can gain 3 Claims. (Cl. 260309.6) trance into the mixing vessel can cause a tenfold increase l in the viscosity. The agent is added in amounts sufficient This invention relates to compositions containing a COIT1- 10 to react with substantially all of the metallic impurities P Compound having a plurality of imidaZOline Tings present in the reactants and generally between about 0.1 as a principal constituent. In another aspect it relates percent to 0.5 percent by weight based on the total weight to a method for preparing such compositions by contactof the acids and amine has been found satisfactory. Suiting a plurality of diverse carboxylic acids and a polyable agents include the alkali metal polyphosphates, such ethylene polyamine under reactive conditions. as sodium and potassium tripolyphosphate.

Monoimidazolines, such as undecylimidazoline, and di- Th mixtu i then heated at 1 atmosphere to about imidazolines, such as octamethylene diimidazoline, are 150 C, t hi h point the pressure and temperature are kn wn but h limit d u i i y- The C mP P Y- adjusted periodically in inverse relationship according to imidazoline of this invention has a high molecular weight, th f llo ing schedule:

is strongly basic, and possesses strong surface activity. 20 When incorporated with a polymeric material, such as Polymers and copoiymer's of vmyl chloride it Performs Heating period in minutes after Temperature, Pressure, admirably as a curing agent. reaction mixture has reached 150 0. 0. mm. Hg

The present compositions are prepared by heating oleic at 1 and sebacic acids and triethylene tetramine at reduced r pressures under nitrogen while vigorously agitating the 21 322 reactants. Imidazoline formation proceeds essentially in 335 two steps. In the first step, a terminal amino group of 181 29? the polyamine reacts with a carboxyl group to form an 1915 110 202.5 85 amide with the release of one mole of water. Then, a 2125, second mole of water splits out from the amide group 220 15 and a secondary amino group beta to it, causing cyclization to give an imidazoline. Dicarboxylic acids reacting with polyamines in this manner produce a complex poly- Since Water catalyzes side reactions and hydrolyzes imimidazoline containing imidazoline rings plus some amide 35 idazolines, it is removed as it is formed in order to groups and secondary amino groups resulting from inachieve maximum conversion to imidazoline. The above complete cyclization. The reaction yields amixture comschedule permits removal of Water as fast as possible prising a major amount of (l) a polyimidazoline having consistent with imidazoline conversion without distilling the following idealized structure: appreciable amounts of tetramine. During the reaction C 7H33 C-NCHzCHzNCCsH s -CNCH2CH2-N-OC 7I-Is3 l-N CH2 The 1% J 1 1 iHz H26 N CH2 CH2 5 CH2 CH2 in which up to about 20 percent of the original carboxyl period, the agitator should be run at a high rate of speed groups are in the form of unconverted amides to give a high surface turnover of the mixture for rapid O H water removal. An agitator speed of about 100-200 l l i CH CH r.p.m. has been found -to be satisfactory. Experiments T have shown that low water removal caused by decreasing derived from the l'fiaction of acid with P y amine the speed from about 150 to 65 rpm. lowered the im- E 1 and/or N'substituted amides idazoline content by about 10 percent due to irreversible R hydrolysis of the imidazoline ring.

g l After a temperature of about 220 C. and a pressure h 1 of about 15 mm. Hg have been reached within three f f m elther ydm ys 1s of prev lousl y formed hours according to the foregoing schedule, the pressure idazoline rings or the reaction of acid with secondary d/ 2 f d and temperature are held at these values and the reaction amme groups an or Specles o azomes an is continued for about one hour. Thereafter the product polyimidazolines having high?- and W .molecular is cooled to 150 C. under nitrogen and collected. The ig i the molecular Welght of the ldeahzed poly' viscosity of the reaction product averaged about 100,000 um azome Structure centipoises at 60 C. The average composition as de- In carrying out the invention, the oleic acid is first charged to a mixing vessel and then the sebacic acid is stirred in. Agitation is continued throughout the reaction period. The acid mixture is deoxygenated at a pressure of about 15 mm. Hg, the vacuum is released with nitrogen and a blanketing stream of nitrogen is thereafter used throughout the reaction. Following deoxygenation, the acids are heated to about C., the

termined by infrared absorption analysis is comprised of structures resulting from about percent conversion of the carboxyl groups to imidazoline rings with the remaining 20 percent of the carboxyl groups existing as amide groups. The average molecular weight of the reaction product ranges between about 3,000 to 4,500 as against about 2,000 based on the idealized polyimidazorequisite amount of triethylene tetramine is added and the line Structuretemperature rises to about C., due to salt formation. 70 The molar cluamlhles of aCldS and amme usfifd f Immediately after adding all of the triethylene tetrapare the reac ion mixture are 2 moles of oleic acid, 5

mine, the system is protected during synthesis against moles of sebacic acid and 6 moles of triethylene tetramine.

Example 1 49.0 lbs. (.17 mole) of oleic acid were charged to a glass vacuum vessel and then 87.6 lbs. (.43 mole) of sebacic acid were added thereto. The acids were heated to about 70 C. and then 76 lbs. (.52 mole) of triethylene tetramine were added. Due to the exothermic nature of the reaction between the amine and acids, the temperature of the mixture rose to about 100 C. 0.213 lb. of powdered sodium tripolyphosphate was then added as a metal chelating agent. Vigorous agitation and a nitrogen atmosphere were maintained throughout. The mixture was then heated at 1 atmosphere to about 150 C. and the temperature and pressure were carefully controlled thereafter for a four-hour period according to the pressure-temperature schedule set forth hereinbefore. During this period, water of condensation was continuously removed to avoid hydrolysis of the imidazolines. The amount of water removed over the entire reaction period corresponded with about 80 percent conversion of the carboxyl groups to imidazoline groups, leaving a balance of about 20 percent of the carboxyl groups in the form of amides. The composition of the reaction mixture was confirmed by infrared absorption analysis. Finally, the product was cooled under nitrogen to about 130 C.

The utility of the reaction product is demonstrated in the following Example 2 in which all parts are reported on a weight basis:

Example 2 Two parts of a reaction product prepared according to the procedure of Example 1 were added to 90 parts of paste grade polyvinyl chloride, 5 parts of epoxidized soybean oil, 18 parts of calcium carbonate, and 5 parts of zinc oxide. This formulation was thoroughly milled at 149 C. until smooth, then sheeted out and press-molded into test specimens. The specimens were cured in 4 minutes at 193 C. giving a thermoset polymer. Properties of the cured polymer were as follows:

Tensile strength at room temp., p.s.i 7200 Tensile strength at 93 C., p.s.i 3500 Percent creep at 121 C./ p.s.i. load 10 These results indicate that the curing action of the re action product of this invention definitely improves temperature resistance of rigid polyvinyl chloride products. The thermosetting character of this polymer renders it useful in such applications where resistance to deformation at elevated temperatures is a prime criterion.

Five ZOO-lb. batches of the triethylene tetramine-acids reaction product were prepared according to the procedure described in Example 1. The compositions of the resulting products as determined by infrared analysis were comprised of structures with 79-82 percent (average 80 percent) conversion of the carboxyl groups to imidazoline rings and the remaining 1821 percent of the original carboxyl groups existing as amide groups.

We claim:

1. A composition derived by reacting in a deoxygenated system 2 moles of oleic acid, 5 moles of sebacic acid, and 6 moles of triethylene tetramine at a temperature of about 50 C. to 240 C. and a pressure of about 10 to 760 mm. Hg while continuously removing the water of reaction, and continuing the reaction until the flow of water of reaction substantially ceases.

2. A composition according to claim 1 wherein the reaction is carried out in the presence of a small amount of a chelating agent.

3. A composition according to claim 2 wherein the chelating agent is sodium tripolyphosphate.

References Cited in the file of this patent UNITED STATES PATENTS 2,374,354 Kaplan Apr. 24, 1945 2,568,876 White et al. Sept. 25, 1951 2,668,165 Carpenter Feb. 2, 1954 2,846,440 Hughes Aug. 5, 1958 2,916,376 Stromberg et a1. Dec. 15, 1959 

1. A COMPOSITION DERIVED BY REACTING IN A DEOXYGENATED SYSTEM 2 MOLS OF OLEIC ACID, 5 MOLES OF SEBACIC ACID, AND 6 MOLES OF TRITHYLENE TETRAMINE AT A TEMPERATURE OF ABOUT 50*C. TO 240*C. AND A PRESSURE OF ABOUT 10 TO 760MM. HG WHILE CONTINUOUSLY REMOVING THE WATER OF REACTION, AND CONTINUING THE REACTION UNTIL THE FLOW OF WATER OF RACTION SUBSTANTIALLY CEASES. 